An electrochemical quartz crystal microbalance study of a prospective alkaline anion exchange membrane material for fuel cells: Anion exchange dynamics and membrane swelling

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[1] John, Jimmy
[2] Hugar, Kristina M.
[3] Rivera-Meléndez, Johary
[4] Kostalik, Henry A.
[5] Rus, Eric D.
[6] Wang, Hongsen
[7] Coates, Geoffrey W.
[8] Abruña, Héctor D.
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Abruña, H.D. (hda1@cornell.edu) | 1600年 / American Chemical Society卷 / 136期
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A strategy has been devised to study the incorporation and exchange of anions in a candidate alkaline anion exchange membrane (AAEM) material for alkaline fuel cells using the electrochemical quartz crystal microbalance (EQCM) technique. It involves the electro-oxidation of methanol (CH3OH) under alkaline conditions to generate carbonate (CO32-) and formate (HCOO-) ions at the electrode of a quartz crystal resonator coated with an AAEM film; while simultaneously monitoring changes in the frequency (Δf) and the motional resistance (ΔRm) of the resonator. A decrease in Δf; indicating an apparent mass increase in the film; and a decrease in ΔRm; signifying a deswelling of the film; were observed during methanol oxidation. A series of additional QCM experiments; in which the effects of CH3OH; CO32-; and HCOO- were individually examined by changing the solution concentration of these species; confirmed the changes to be due to the incorporation of electrogenerated CO32-/HCOO- into the film. Furthermore; the AAEM films were found to have finite anion uptake; validating the expected tolerance of the material to salt precipitation in the AAEM. The EQCM results obtained indicated that HCOO- and CO32-; in particular; interact strongly with the AAEM film and readily displace OH- from the film. Notwithstanding; the anion exchange between CO32-/HCOO- and OH- was found to be reversible. It is also inferred that the film exhibits increased swelling in the OH- form versus the CO32-/HCOO- form. Acoustic impedance analysis of the AAEM-film coated quartz resonators immersed in water showed that the hydrated AAEM material exhibits significant viscoelastic effects due to solvent plasticization. © 2014 American Chemical Society;
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